Acid fading inhibition



United States Patent ACID FADING ITION Julius Eisele, Ludwigshafen (Rhine), Wilhelm Federkiel,

Frankenthal (Pfalz), Germany, Ernst Wilhelm Gassenmeier, deceased, late of Mannheim, Germany, by Ruth Martha Gassenmeier, heir and guardian of minor heirs, Mannheim, and Curt Schuster, Ludwigshafen (Rhine), Germany, .assignors to Badische Anilin- & Soda-Fabrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany N Drawing. Application March 30, 1953, Serial No. 345,688

Claims priority, application Germany April 3, 1952 6 Claims. (Cl. 861) This invention relates to improvements in the dyeing of textile materials containing organic derivatives of cellulose (i. e. cellulose esters and ethers, such as cellulose acetate, ethyl cellulose, and the like), whereby the dyeings thereon are rendered fast to acid fading (also known as atmospheric or gas fading).

Many of the water-insoluble dyestuffs yielding desirable shades on organic derivatives of cellulose in textile materials, and having satisfactory fastuess to light, washing and other agencies, have been found to be sensitive to fading upon prolonged exposure to acid fumes, particularly the gaseous combustion products of coal, gas and other fuels, which are present in minor concentration in the atmosphere, particularly in urban communities. In some cases, the brightness of the dyeing is dulled, while in others a marked change in the shade of the coloration occurs. This is especially true of dyeings produced with anthraquinone dyes, particularly thoseyielding valuable blue dyeings on organic derivatives of cellulose. When textile materials dyed with these compounds are'exposed to acid fumes, the coloration changes to one of a reddish or brownish cast, and on continued exposure may change to a pink coloration. This effect limits to a considerable extent the usefulness of such dyestuffs, which are otherwise highly satisfactory. Sensitivity to acid fumes is not restricted to anthraquinone dyes, but is likewise noticeable in the case of dyestuffs belonging to other classes.

Numerous proposals have been made to overcome acid fading, ordinarily involving the application to textile material of compounds or compositions intended to prevent such fading of the coloration. Such compounds or compositions are referred to herein as acid fading inhibitors.

For commercial use, an acid fading inhibitor should be colorless, adapted to withstand prolonged exposure to light and/ or combustion gases without discoloration, fast to dry-cleaning and wet-washing, odorless, and non-toxic in the sense that it causes no skin irritations when materials treated therewith are worn. While most of the acid fading inhibitors heretofore proposed satisfy a number of these requirements, in most cases they are defective in some of said requirements, whereby their usefulness is considerably impaired.

We have discovered that certain cyanoalkylamines, specifically colorless, fully saturated, from 3 to 7 membered mononitrogen heterocyclic compounds, and amines having cycloaliphatic radicals in their molecule, having attached to nitrogen at least once a cyano-alkyl-group from 1 to 10 carbon atoms are highly effective acid fading inhibitors when incorporated in minor amounts to textile materials containing organic derivatives of cellulose colored with organic dyestufis.

Suitable compounds of said kind may be generally obtained by reacting amines or imines with aliphatic aldehydes and hydrocyanic acid or with aliphatic halogencyano-compounds or with cap-unsaturated aliphatic ni- 2,813,773 Patented Nov. 19, 1957 2 triles such as acrylonitrile, u-methylacrylonitrile (methacrylonitrile) or fl-methylacrylonitrile.

Specifically suitablecompounds are obtained for instance by these reactions with ethyleneimine, spirocyclohexylethyleneimines, pyrrolidine, piperidine, hexamethyleneimin'e, cyclohexylamine, alkylcyclohexylamines, diamino-dicyclohexylamine, diarnino-cyclohexane, amino-, tetraor decahydonaphthalenes, aminodecahydrodiphem yls, 2 aminoethyl 3,3'-dimethyl-norcamphane, 4,4'-diamino dicyclohexylmethane, 4,4-di-(mono-w-aminopropylamino-)-dicyclohexylmethane, 4,4 di (monoethylamino-)-dicyclohexylmethane and 4,4'-diamino-dicyclohexylamine.

The incorporation of the inhibitors of the present invention in the organic derivatives of cellulose may be carried outby several methods.

On account of the high natural afiinity of the acid fading inhibitors ofthe invention for organic derivatives of cellulose the application of said inhibitors to textile material of this kind may be carried out by treatment of the goods with an aqueous dispersion of the inhibitors before or after the dyeing, but is most conveniently and economically carried out simultaneously with the dyeing. Thus, the inhibitors can be dispersed in the aqueous bath by any of the methods commonly used for similar dispersion of water-insoluble dyestuffs.

A further method to apply the inhibitors to the textile material consists in treating the textile material in an aqueous bath contaiuing said inhibitors in form of theirformaldehyde bisulfite compounds which may be easily prepared from the inhibitors by reacting them with formaldehyde and sodium bisulfite. These products dissolve readily in cold water, but when the aqueous solu tion thereof is heated as is the case in the dyebath, they are decomposed slowly to yield back the water-insoluble initial material. Thus, the inhibitors may be introduced into the textile material in a water soluble form to split in the textile material to the water-insoluble compound. It is of no damage if the water-soluble inhibitor is already partly split in the bath, since the very finely divided waterinsoluble inhibitor thus obtained goes readily to the tex tile material.

Another method to incorporate the water-insoluble inhibitors in the material consists in dissolving them in a spinning mass of the organic esters of cellulose and performing the spinning process as usual, which is not disturbed in any way since the inhibitors are readily soluble in the spinning mass.

The amountof acid-fading inhibitors of the invention which can be employed may be varied within rather wide limits. Thus, we have found them to be fully effective in amounts corresponding to about 0.1 to 3%, especially about 1% by weight, calculated on the quantity of organic derivatives of cellulose employed. In some cases it maybe of advantage to use higher quantities, whereas in other cases lower amounts may be satisfactory.

The following examples wherein parts and percentages are by weight illustrate the manner in which a number of acid fading inhibitors of our invention can be used.

EXAMPLE 1 100 parts of a cellulose acetate rayon fabric are tested at C. for 1 hour in 2000 parts of water containing 1 part of finely divided 1.4-di-(monomethylamino-)anthraquinone and 1 part of the following compound as a preparation with the condensation productof lmol e A j 2,813,773

ofsp'ermic oil al'cohol and 24 mols of ethylneoxide. The dyed fabric is then soaped,.rinsed,.and dried as usual. There is obtained a bright blue dyeing which shows an excellent resistance to acid fumes whereas the dyeing. obtained in the absenceof? the N=w-cyano'-'ethylspirocyclohexylethyleneimine turns red shade after being a short'timein an acid fume containing atmosphere.

EXAMPLE 2' 100 parts of-a cellulose acetate rayon fabric are'treated in 2000 parts of'water containing 0.3 partof finelydivided 1L4-diamino-anthraquinone-and 1 part of'the finely dispersed compound H kT-CHrCHg-CN at 75 C. for 1 hour. There is obtained a violet dyeing which shows an'excellent resistanceto acid fumes.

EXAMPLE 3- 100 parts of a cellulose acetate rayon fabric are dyed' EXAMPLE 4 1000 parts of a celluloseacetate rayon fabricare treated in 15g000 parts of water containing 5 parts of finely dispersed 1 amino 4-methylarnino-anthraquinone Z-carboxylic acid amide and 15 parts of the finely dispersed inhibitor -CH9CHT-ON H @l CH2'-CHz-UN at 75 C. for 1 hour. The dyed fabric is then rinsed'and' dried as usual. The resultingbright blue 1 dyeing shows a complete resistance to acid fumes.

The same result is obtained by employing-'the'mhibitor instead of the inhibitor used in the foregoing paragraph.

EXAMPLE '5 1000 parts of a cellulose acetate: rayon fabric are treated in 15,000 parts of water containedS parts of finely dispersed 1-arnino-4-methylamino-anthraquinone 2 carboxylic acid amide 'and 15 parts of the finely. dispersed inhibitor of the formula:

CH3 H at 75 C. for 1 hour. The blue colored fabric thus obtained shows an excellent fastness to acid-fading.

EXAMPLE 6 1000 parts of a cellulose acetate rayon fabric are treated in.15,000 parts of water. containing parts of finely dispersed 1-amino-4-methylaminO-anthraquinone Z-carboxylic acid amide and 15v parts ofthefinely. dispersedin hibitor of the formula /CH2CHr-CN T N i V CHz-CN at 75 C. for 1 hour. The dyed fabric is made up as usual. There is obtaineda bright blue colored fabric which shows an excellent fastness to gas-fading.

The, inhibitor of='the'foregoing paragraph can be replaced by the following compound GHQ.

EXAMPLE 7 1000 parts'of a cellulose acetate rayon fabric are treated at 75 C. for'l hour in 2000 parts of water containing 0.3 part of. finely dispersed 1.4-diamino anthraquinone CHr-CHz-OH andl part of the water-soluble formaldehyde-bisulfite' corn'pound'of the inhibitor H N-C Hz CHz-C N (obtained by treating lrnol of the inhibitor with Zmols ofsodium hydrogen sulfite and 2 mols of formaldehyde).-

Thereis obtained 'a-violet colored fabric which shows a very good-fastness' to gas-fading.

EXAMPLE 8 In a spinningsolution of acetyl cellulose in acetone is dissolved the inhibitor CH2 v N-cH1-+oH-'CN in'amounts corre'sponding to 2.5 percent-related to dry acetyl cellulose. After spinning this solution in the usual way cellulose acetate-rayon is obtained-which'is dyed with 1 percentof l.4-di'-'(inonomethylamino-)anthra quinone in known-manner; There-are thus obtained-vivid" blue-colored rayons which are-very fast to gas-fading;

EXAMPLE 9 1000 parts -of-a cellulose acetate rayon fabric aretreated' at'75 C. forl 'hour'in' 15,000 parts of water containing 15 parts of finely dispersed 1-rnetl1ylamino-4-hydr'oxy-' e ylamino-anthraqninone and 15 parts of the finely dispersed inhibitor of the following formula (obtained by reacting 1 molof 4'.4'-diarnino-dicyclohexyl methanewithZ mols of iu-chlorovaleronitrile).

Thereis obtained a'blu'ecolored fabric which 'shows-ani excellent fastn'ess to gas-fading.

Instead of the inhibitor of the foregoing paragraph the same amounts of the inhibitor of the formula (obtained by reacting 1 mol of 4.4'-diamino-dicyclohexylmethane with 2 mols of w-bromo-w'-cyano-decan) may be used.

EXAMPLE 100 parts of a mixed fabric of cellulose acetate rayon and viscose rayon are treated at 75 C. for 1 hour in 5000 parts of Water containing 2 parts of finely dispersed l-amino-4-hydroxyanthraquinone and 3 parts of finely dispersed inhibitor of the formula 100 parts of acetate cellulose rayon fabric are treated in 2500 parts of water containing 1.5 parts of finely dispersed 1.4-diamino-5-nitro-anthraquinone and 3 parts of one of the inhibitors Nos. 1 to 22 listed in the following table at 75 C. for 1 hour.

There are obtained violet colored fabrics which show an excellent fastness to gas-fading.

Table No. Inhibitor CH: H H /CH: NCO

( JN CH,

\ H H /CHa AN CHz CHr-CH:

/ CHrCHr-CN i om-om CHg-CHz-CN @nwm-om-or:

No. Inhibitor H HxO-C H 1 l@N.GH:CHr-ON CHa-OHOH2 H s Ea @nrwm-om-orr CH;OH CH-CH2 H 9 H; N-oH,-ornoN H H 10 NC-OH -CHa-N NCHi-CH:CN

11 N-CHr-CHz-CN g-cmwm-cn V NCH-CH2CN N-'CHa-CN ,H

H N-CHa-CHz-CN 14 n V H NCH2CH:ON 15 u H N-CHr-CHa-ON H N-CHn-CHz-CN H @NOH:CN 17 N H N-CHr-CN N-CHz-CHz-ON 18 CH1 CHr-CHz-CHI CH:CH1NCHrOHr-CN om-om-om CHI-CHI-N-CHICN 21 H N-OHpQHPQN 22 H N:-CHrCN 23 H N-cH-oN What we claim is:

l. A process for improving the fastness of colorations of'water-insol-ubl dyestuffs on organic drivativesof cellulose textile material'toacid fading which comprises incorporating in such material' the compound of the formula 2. A process for improviug -the fastness of colorations of water-insoluble dyestufis on-"cellulose acetate textile materialito acid fading-whichcomprisesincorporating in such,

material the compound of the formula 3. Textile materiai' coriiprisingdyed fibres of an organic derivative of cellulose dyed with a water-insoluble dyestuif having incorporated therein the compound of the.

formula C Hf 4. Textile material comprising dyed fibres of cellulose acetate dyed with a water-insoluble dyestufl having incorporated thereintherompound of the formula 5. An improved process for improving thefastness of coloration's of""Waiter insoluble"dyestuffs on cellulose acetate textile material to acid fading by incorporating in such material a water-insoluble colorless basic inhibitor, said improvement comprising using as inhibitor a compound of the general formula 6'1 -Textile material comprising fibers of cellulose acetate dyed with aWater-insolubleorganic dyestuff and/having incorporated therein a water-insoluble colorless basic inhibitor of the general formula wherein R represents a member of the classconsis'ting of hydrogenand lower 'alkyl groups and c X represents a divalentj radical selected from theclass consisting of saturated linear and branched alkylenegroup containing from 1 to 10 karbon atomsw keferencesfiited in the =file of this patent UNITEDSTATES' PATENTS Ellis Oct. 15, 1935 Grimmel Nov. 14, 1935 OTHER-REFERENCES Sill'lou'rnal and Rayon World for November 1945, page Strob'el' Ian. 23; 1951' 

1. A PROCESS FOR IMPROVING THE FASTNESS OF COLORATIONS OF WATER-INSOLUBLE DYESTUFFS ON ORGANIC DERIVATIVES OF CELLULOSE TEXTILE MATERIAL TO ACID FADING WHICH COMPRISES INCORPORATING IN SUCH MATERIAL THE COMPOUND OF THE FORMULA 